Chemo-, regio-, and stereo-selective perfluoroalkylations by a Grignard complex with zirconocene. Issue 45 (6th October 2015)

• Record Type: Journal Article
• Authors: Fujiu, Motohiro; Negishi, Kazuyuki; Guang, Jie; Williard, Paul G.; Kuroki, Shigeki; Mikami, Koichi
• Is Part Of: Dalton transactions. Volume 44:Issue 45(2015)
• Page Start: 19464
• Page End: 19468
• Publication Date: 2015-10-06
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt03039k
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The unique reactivity and high selectivity of the zirconocene-hybridized heterobimetallic perfluoalkyl Grignard reagents can be employed for efficient and highly selective nucleophilic perfluoroalkylation of carbonyl compounds and epoxides, in particular. Abstract : The synthesis of highly reactive perfluoroalkyl Grignard reagents with early transition metal zirconocene complexes and their new types of highly chemo-, regio-, and stereo-selective perfluoroalkylation reactions are reported with epoxides in particular. The zirconocene complex is advantageous in activating the perfluoroalkyl Grignard species. The zirconocene·Grignard complexes were clarified by DOSY. Both 1 H and 19 F DOSY analyses show that the addition of MAO and dioxane to the mixture of RF MgCl and Cp2 ZrCl2 connects Cp2 Zr and RF Mg to generate the zirconocene/perfluoroalkyl-Grignard/dioxane complex.